Compositions comprising succinyl half esters



United States Patent Ofiice 3,370,958 Patented Feb. 27, 1968 Claims.(Cl. 9991) The present invention relates generally to half esters ofsuccinic acid of a mono-acylated polyalcohol, having particular utilityin baked goods and, more particularly, it relates to baked goodsutilizing half esters of succinic acid of a mono-acylated polyalcohol.

This application is a divisional application of application Ser. No.395,013 filed Sept. 8, 1964, Patent No. 3,- 293,272, which was acontinuation-in-part of application Ser. No. 174,266 filed Feb. 19,1962, the latter being now abandoned.

It is known that the addition of certain polyalcohol derivatives toedible fats and oils improves the properties of fats and oils in cakes,bread, and other baked goods. By way of example, the volume and textureof baked goods, which include liquid or plastic shortenings, areimproved by the presence of monoand diglycerides, and glycerol lactopalmitate.

It is known to add various chemical compounds, dough conditioners orother agents in connection with the bark ing of various goods and,generally, these materials have been added to provide improvement in thestructural characteristics of the baked goods, such as their grain andtexture, to provide softer or moister baked goods, or to provide bakedgoods of increased volume. Also, these materials have been added toimprove the handling characteristics or machineability of the doughprepared for the baked goods. Generally, the previously known materialswhich have been added have not provided improvement in all of thesecharacteristics, but have only provided improvement in one or two ofthese characteristics, or the material has provided an undesirable tasteor flavor in the baked goods.

It is a primary object of the present invention to provide a half esterof succinic acid and of a mono-acylated polyalcohol. For convenience,these compounds of the invention will be referred to herein as succinylhalf esters. It is a more particular object of the present invention toprovide semi-succinic acid esters of monoglyceride. This compound willbe referred to herein as succinylated mono-glyceride (SMG).

A further object of this invention is the provision of succinyl halfesters as improvers of baked goods and, more particularly, forimprovement in baking bread.

An additional object of this invention is to provide succinyl halfesters in combination with edible fats and oils, and particularly thosefats and oils used in baking. In this connection, it is an object ofthis invention to provide an improved liquid shortening which includessuccinyl half esters.

Another object is to provide succinyl half esters in combination withother food emulsifiers in the presence of fats or oils used in baking.

A further object of the invention is to provide salts of succinyl halfesters and a more particular object is to provide such salts which arewater soluble.

It is another object of this invention to provide the succinyl halfesters in such form as to more readily improve baking properties invarious formulations.

A still further object of this invention is the provision of processesfor making succinyl half esters.

Other objects and advantages of the present invention will be comeapparent by reference to the following description.

The compound of this invention is a half ester of succinic acid and of amono-acylated polyhydric alcohol, or its salt. This compound or its saltmay be represented by the following general formula:

A(OH),,' (F (SCOOM) in which compound F is a residue of an evennumbered, straight chain saturated fatty acid having from 14 to 24carbon atoms; SCOO is the succinic acid residue or the salt thereof; Ais a residue of a polyhydric alcohol having a straight chain length offrom 2 to 6 carbon atoms; In is equal to l; n is a number from zero to4; and M is hydrogen, an edible alkali metal or alkaline earth.

In the preferred embodiment, stearic acid is the fatty acid residue inthe compound of this invention, but myristic, palmitic and behenic acidsprovide satisfactory residues. The fatty acid residue should besubstantially completely hydrogenated and the unsaturated fatty acidresidues, such as oleic and linoleic acid residues, have not been foundto be effective compounds for purposes of this invention. Also, in thepreferred embodiment, the polyhydric alcohol residue is a glycerolresidue, thus providing a free hydroxyl group on the glycerol residue.However, a propylene glycol residue in the compound of the inventionprovides a compound having no free hydroxyl group and which is asatisfactory compound. On the other hand, sorbitol or sorbitan providecompounds having two or more free hydroxyl groups and which aresatisfactory compounds.

In the preparation of the succinyl half esters, succinic acid ispreferably utilized in itsanhydride form. The preparation of thecompoundof this invention is controlled to provide a low degree ofpolymerization and to maximize the half ester content of the succinylhalf ester.

If the reactants utilized in the preparation of succinyl half esters aresubstantially pure and the preferred conditions for reaction areutilized then the resulting product will be predominantly succinyl halfester. On the other hand, if the reactants are not substantially pureand/or the preferred reaction conditions are not employed, then somebyproducts are formed thereby providing a mixture. The compound of theinvention has been found to be effective regardless of the presence ofsuch byproducts as saturated and unsaturated triglyceride compounds,full or neutral esters and di-acylated polyhydric alcohol derivatives.These byproducts have been found to have little functional activity inbaked goods and the mixture must be added in such amounts as to providea sufficient amount of the succinyl half ester.

The succinyl half esters with a free hydroxyl group have low solubilityin vegetable oil at room temperature while the succinyl half esters ofpropylene glycol are much more soluble in oil at room temperature. Thesuccinyl half esters may be solubilized in oil at elevated temperaturesabove the melting point of the succinyl half esters.

1" However, all of the succinyl half esters have low solubility in waterat room temperature. The water solubility of the succinyl half esterscan be very substantially increased by forming alkali salts of thesuccinyl half esters. These salts provide several advantages in theutilization of the succinyl half esters in baking.

The succinyl half esters can be slurried in water, preferably in thepresence of a coemulsifier. In this connection, I have found that ionicsurfactants are effective coemulsifiers, in minor amounts, to provide aslurry of succinyl half esters. Such ionic surfactants are soap, e.g.,sodium stearate, and sodium salts of succinylated monoglyceride. I havealso found that noni'onic emulsifiers, e.g. monoglycerides, sucrosernonopalrnitate, and polyethoxylated stearic acid, are not particularlyeffective for providing slurries of the succinyl half esters.

In the preparation of the succinyl half esters, the monoacylatcdpolyhydric alcohol can be prepared by esterii cation of the polyhydricalcohol, e.g., glycerol, with a fatty acid having an even chain lengthof from 14 to 24 carbon atoms, which is preferably stearic acid. In thisconnection, the fatty acid is reacted with the polyhydric alcohol undersuch conditions that the polyhydric alco hol is present in a substantialexcess in order to assure provision of a preponderance of monoacylatedcompound.

It will be understood that various amounts of di-esters or tri-esters ofthe higher fatty acid and polyhydric alcohol may be present with themono-esters. I have found that the presence of these polyester compoundsdoes not provide compounds or derivatives which are functional toimprove the overall baking properties. Since, in an equilibriumreaction, the esterification will provide about 60 percent mono-acylatedester and about percent of the di-acylated ester, the reaction mixturedesirably is molecularly or otherwise distilled to enrich the mixture inmono-acylated ester. The succinyl half ester is desirably prepared witha mono-acylated ester content of not less than about percent and,preferably, the succinyl half esters are prepared with molecularlydistilled monoacylated ester wherein the rnono-acylated ester is presentat a level of at least about 90 percent.

The mono-acylated ester of the polyhydric alcohol is then preferablyreacted with succinic anhydride, although succinic acid may be used,under suitable conditions. These reaction conditions are so controlledas to provide maximum amounts of the half ester of the acid, asdistinguished from the full or neutral ester, and to minimizepolymerization. This control is effected by measurement of the acidnumber and by termination of the reaction when the acid number is aboutone-half of the original acid number of the reactants. In thisconnection, each molecule of the succinic anhydride is reacted with onemolecule of the mono-acylated polyhydric alcohol at one of its hydroxylgroups. If the reaction conditions are not suitably controlled, the freecarboxyl groups on the half ester are reduced and the yield of thesuccinyl half ester is reduced.

For economic purposes, the half ester content of the mix produced by thereaction should be at least equal to the full or neutral ester contentof the mixture. Thus, the mixture of esters should comprise at leastabout 50 percent succinvl half ester.

The succinyl half esters may be added at various points in thepreparation of baked goods and it has been found that they arefunctional in baked goods, whether or not other fatty substances arepresent. Thus, the succinyl half esters may be added in the preparationof baked goods, in the presence or absence of fat. It has been foundpossible to add the succinyl half esters to the flour which is used inthe preparation of baked goods, but, of course, the succinyl half estersmay be added to fats or oils used in the preparation of baked goods. Inaddition, the succinyl half esters and particularly the salts of thesuccinyl half esters may be added to aqueous ingredients utilized in thepreparation of baked goods.

The succinyl half esters have been found useful in shortenings and canbe added to a fat or oil having plastic flow characteristics or havingNewtonian flow characteristics. In this connection, a shortening may beprepared by adding the succinyl half ester to a liquid oil, such ascottonseed oil, soybean oil, or peanut oil, and also by adding to suchoil a hard fat, such as cottonseed stearine, and/or an emulsifier likemono-glycerides and lactylated glycerides.

The level of the succinyl half ester in the shortening should be such asto provide functional amounts in the baked goods in which the shorteningis used. In liquid shortening, it has been found that, in the absence ofother emulsifying materials, the succinyl half esters of monoacylatedproplyene glycol, which are the only succinyl half esters havingsubstantial solubility in oil, may be used at levels up to the level oftheir solubility and to give functionality are present in the oil atlevels of more than 3.5 percent. When co-emulsifiers are present, theother succinyl half esters may be incorporated into the oil and improvedcake baking results have been observed. The combination of the succinylhalf ester and its coemulsifier should comprise at least about 4 percentof the liquid oil.

It has also been found that improved cake baking results are achievedwhen the succinyl half ester is present in plastic shortenings at levelsof at least about 2 percent, when it is present in the absence ofcoemulsifiers, but it has also been found that lesser amounts ofsuccinyl half esters may be employed when coemulsifiers are used,provided that the mixture of succinyl half ester and coemulsifier ispresent in plastic shortening at a level of at least about 2 percent.

In bread baking, it has been found that the presence of .1 percent ofthe succinyl half ester in bread, based upon the weight of flour,provides improved grain and texture and when it is present in bread atlevels in excess of .2 percent, based upon the weight of flour, there isimproved softness and a moister bread product is provided.

The presence of the succinyl half ester has also been found to provideimproved machineability of bread dough and increased bread volume. Inaddition, the succinyl half ester, when used in bread dough, does notgive any undesired taste or flavor to bread. Certain doughs, for eX-ample dietary bread dough, have been prepared without utilizing fat andit has been found that the succinyl half ester provides improvement inthe grain, texture, softness, and volume. In this instance, of course,the succinyl half ester functions independently and effectively in thefatfree dough,

As above indicated, the succinyl half ester provides improvements incake and bread baking and, generally, will be used after it isincorporated in the shortening, whether liquid or plastic shortening.However, the alkali salts of the succinyl half ester may be added toflour in the preparation of cakes.

As above indicated, the succinyl half esters should not provide anoticeable flavor in baked goods and should be bland in flavor. Whileeffective succinyl half esters can be prepared in various ways andwashed or treated, it has been extremely diflicult to provide a blandflavored product. I have discovered a particular method formanufacturing the succinyl half ester which provides a bland flavoredproduct and which product can be used in baked goods without impartingany undesired flavor.

I have found that a substantially bland tasting succinyl half ester maybe prepared when the reaction between the mono-acylated polyhydricalcohol and succinic anhydride is carried out at a temperature below themelting point of succinic anhydride. While the exact reason forproviding this bland taste is not wholly understood, it is believed thatwhen the reaction temperature is maintained below the melting point ofthe succinic anhydride, undesired self-condensation of the succinicanhydride leading to the formation of hydrochelidonic acid, or itsanhydride, is avoided.

In carrying out this process, the mono-acylated polyhydric alcohol, suchas a monoglyceride, is heated to a temperature suflicient to melt themono-acylated polyhydric alcohol, but, after it is melted, thetemperature should be adjusted to below the melting point of succinicanhydride which is then suspended in the molten monoacylated polyhydricalcohol. The reaction commences under heterogeneous phase conditions andthe phases change to a homogeneous mass as the reaction proceeds tocompletion.

The reaction is preferably effected under an inert atmosphere withstirring and the reaction is allowed to proceed to completion of thehalf ester or until the free succinic anhydride is used up. Themono-acylated polyhydric alcohol and succinic anhydride react insubstantially equimolar concentrations. However, the monoacylatedpolyhydric alcohol may be present in some excess, and the excess acts asdiluent. In order to limit formation of reactions which may result inundesired flavors, the reaction is carried out at a temperature belowabout 115 degrees C., but above the melting point of the mono-acylatedpolyhydric alcohol.

As above pointed out, the reaction is preferably carried out underconditions of agitation and under an inert atmosphere, such as anitrogen atmosphere, until a clear homogeneous melt is obtained and thesuccinic anhydride is substantially completely reacted. In the case ofreacting a mono-stearine with succinic anhydride, the reaction proceedsuntil an acid number of less than 135, and preferably less than 125, isobtained. In general, an acid number of less than 125 is obtained aftera period of about A to 3 hours. The clear melt reaction product may bespray chilled, or otherwise cooled to room temperature.

The reaction between the mono-acylated polyhydric alcohol and succinicanhydride at low temperature, for example, those below 95 degrees C.,are advantageously accelerated by the presence of a catalyst in thereaction mixtures, Generally, at temperatures above about 95 degrees C.,the reaction can be carried out in reasonable times without the presenceof a catalyst. I have found an eifective catalyst to include the cationsof alkali metals and/ or alkaline earths. In general, any soluble saltwhose anions are not deleterious to the succinyl half ester may beemployed. Particularly suitable catalysts include alkali metalcarbonates, alkali metal andalkaline earth soaps, alkali and alkalineearth succinatesaad alkali metal and alkaline earth salts ofsuccinylated monoglyceride.

The catalyst is employed in a minor amount, but will be present in anamount from .05 percent to about 2 percent by weight of the reactionmixture. While greater amounts of catalyst can be employed, there is nota great improvement in the reaction. The catalyst has been found mosteffective at levels from about .1 percent to about 1 percent.

The catalyst may be added to the reaction mixture before, during, orafter the succinic anhydride is added to the molten mono-acylatedpolyhydric alcohol. However, the preferred method contemplates additionof the catalyst to the reaction mixture during or after the addition ofsuccinic anhydride.

In the following are set forth various examples in respect to thesuccinyl half ester and their use in baked goods.

Example I As an example of the preparation of the succinyl half esterfor use in the present invention, it is prepared by taking 1,000 partsof hydrogenated lard mono-glyceride, comprising 92 percentmono-glyceride, and placing it in a vessel equipped with an agitator anda nitrogen purge line. The mono-glyceride is heated to about 120 degreesC., and vacuum is applied for a short time to remove free moisture.

240 parts of succinic anhydride is added to the flask with agitation,and the flask is purged with nitrogen. The heat of reaction and addedheat caused the temperature of the reaction mass to rise to about 165degrees C. The reaction mass is maintained at 165 degrees C. for about30 minutes, whereupon it is cooled to about degrees C.

25 parts of a 50 percent aqueous solution of potassium carbonate isadded to the reaction mass, and the mixture is stirred rapidly. Themixture is then exposed to a vacuum of 30 mm. of Hg and stirred for 15minutes in order to remove free moisture.

The reaction product has the following analysis:

Acid number, mg. KOH/ g 91.2 Saponiflcation number mg. KOH/ g. 333.3Melting range, C. 51-58 Iodine value, Wiijs 0.4 Free succinic acidanhydride, weight percent Nil Total bound succinic anhydride, weightpercent 17.3 Succinic anhydride bound as semiester, weight percent 15.0Succinic anhydride bound as neutral ester, Weight percent 2.3

Example II As an additional example of the succinyl half ester in accordwith the present invention, 1,000 parts of distilled hydrogenated lardmono-glyceride, LV. about 1, comprising 92 percent mono-glycerides, 8per cent di-glycerides, and a small amount of tri-glycerides, is chargedinto a gallon stainless steel reactor equipped with an agitator and asteam-heated jacket. The mono-glyceride is heated to degrees C, and thereactor is partially evacuated to remove free moisture from themono-glyceride.

The reactor is purged with nitrogen, and 260 parts of succinic anhydrideis added rapidly with agitation. The resultant heat of reaction andadded heat causes the temperature of the reaction mass to rise to aboutdegrees C., and this temperature is maintained for about 2 hours.

The reaction product is then cooled to about 80 degrees C., and 70 partsof a 50 percent aqueous solution of potassium carbonate is added withagitation. Mixing of the reaction product with the aqueous solution iscon tinued for about 3 minutes at 80 degrees C.

Thereactor is then evacuated to a pressure of about 30 mm. of mercury toremove free moisture, and held at this pressure for about 15 minuteswhile the reaction product is agitated. The reaction product isthereafter pumped from the reactor and spray chilled to providefree-flowing powder.

The reaction product has the following analysis:

Acid number, mg. KOH/g. 76.5 Saponification number, rng. KOH/g. 336.0Melting range, C. 5459 Iodine value, Wiijs 0.4 Free succinic anhydride,weight percent Nil Total bound succinic anhydride, weight percent 17.6Succinic anhydride bound as semiester, weight percent 13.7 Succinicanhydride bound as neutral ester, weight percent 3.9

Example Ill As an additional example of the preparation of succinyl halfester in accord with the present invention, 1,000 parts of hydrogenatedlard mono-glyceride, comprising 92 percent mono-glyceride, is placed ina vessel equipped with a stirrer and a nitrogen purge line. Themono-glyceride is meited by heating the flask to about 120 degrees C.,and vacuum is applied to the flask for a short time to remove freemoisture.

180 parts of succinic anhydride is added to the flask with agitation,and the flask is purged with nitrogen. Ex-

tcrnal heat plus the heat of reaction causes the temperature of thereaction mass to rise to about 140 degrees C. The reaction mass ismaintained at this temperature for about minutes, whereupon it is cooledto about 80 degrees C., and mixed with parts of a percent aqueoussolution of potassium carbonate.

After mixing, the free moisture is removed from the flask by vacuum, andthe resultant reaction product is flaked to provide a chipped product.There is obtained a reaction product having the following analysis:

Acid number, mg. KOH/ g. 74.0 Saponification number mg. KOH/g. 301.4Melting range, C. 52-56 Iodine value, Wiijs 0.6 Free succinic acidanhydride, weight percent Nil Total bound succinic anhydride, weightpercent 13.9 succinic anhydride bound as semiester, weight per cent 13.2Succinic anhydride bound as neutral ester, weight percent 0.7

Example IV As a further example of the preparation of the half ester foruse in the mixture of the invention, 5,000 grams of hydrogenated lardmono-glyceride, comprising 92 percent mono-glyceride, was placed in a 12liter three-necked flask provided With a stirrer and nitrogen purgeline. The product was heated to melt it and free moisture was removed byapplication of vacuum. 1300 grams of succinic anhydride was added, withagitation, under a nitrogen blanket. Ten minutes Were utilized in addingthe succinic anhydride and, after such addition, the flask wascontrolled at 145l50 degrees C. for 45 minutes. At the end of thisperiod, the resulting product was cooled and solidified by pouring itinto porcelain pans.

The reaction product had the following analysis:

Acid number, mg. KOH/g. 106.4 Saponification number, mg. KOH/g. 357.5Iodine value, Wiijs 0.5

Example V As an additional example of the preparation of the half ester,972 grams of propylene glycol monostearate (comprising percentmonoester) was placed in a flask equipped with a stirrer and a nitrogenpurge line. The monostearate was melted, and vacuum was applied to theflask to remove moisture.

'240 grams of succinic anhydride, and 1.5 grams of potassium carbonatewere added to the flask. The potassium carbonate was present toaccelerate the reaction. The flask was purged with nitrogen, and thereaction mass was heated to 165 degrees C. with stirring. The reactionmass was held at 165 degrees C. for about 30 minutes.

The reaction product was removed from the flask and allowed to cool, andwas thereafter suspended in about 10 liters of water. The suspension washeated with vigorous agitation at 65 degrees C., and was thereaftercooled with agitation.

The reaction product solidified in small particles, and was filteredfrom the water and air dried.

The reaction products of certain of the foregoing examples wereevaluated by adding 2.5 percent of each reaction product to a commercialshortening comprising hydrogenated cottonseed oil and not includingmonoglycerides or di-glycerides, and baking standard white cakestherefrom. These cakes were compared to control cakes, hereinaftercalled Control A, baked with a commercial shortening containing about6.5 percent of monoand di-glycerides. A second series of control cakeswere also prepared, hereinafter called Control B, baked with a plasticshortening containing 2.5 percent glycerol lacto palmitate. A thirdseries of control cakes was also prepared, hereinafter called Control C,with a plastic shortening containing 2.5 percent of molecularlydistilled 8 mono-glyceride (92 percent mono-glyceride) derived fromhydrogenated lard.

The cakes comprising the reaction product of the present invention andthe control cakes were prepared in accordance with the followingingredients:

Parts Flour 41.9 Sugar 52.1 Salt 1.0 Baking powder 2.5

To 48.7 parts of the foregoing dry mix there was added 10.0 parts of theshortening and 16.0 parts of fluid whole milk. The dry mix, shortening,and milk were blended well, and to the blend was added a wet mixcomprising parts of egg whites and 8.0 parts of fluid whole milk. Theresultant mixture was blended to provide a satisfactory batter, and thespecific gravity of the batter was measured.

420 grams of the batter was placed in an eight inch cake pan and bakedat a temperature of 350 degrees F. After baking, the volume of the cakewas measured, and the cake profile was determined.

In this connection, the cake profile was determined by measuring theheight of the cake at three points along the diameter of the cake. Acake Was considered to have a desirable profile, if the cake height wassubstantially uniform across its diameter, indicating that the cakeneither had a central depression nor an excessive central hump.

The grain and texture of each of the cakes was also observed.

Table 1 summarizes the results of the foregoing evalnations:

TABLE l.BAKING PERFORMANCE WITH PLASTIC through IV had volumessubstantially equivalent to Control A cakes, comprising a shorteningcontaining 6.5 percent of monoand di-glycerides. It will also be seenthat the volume of cakes comprising the reaction product of the presentinvention were substantially greater than the volumes of Control B and Ccakes, comprising, at corresponding levels, glycerol lacto palmitate,and distilled mono-glycerides, respectively.

Cakes comprising the half ester had good flavor and eating quality. Inaddition, it will be seen that they had excellent profiles, incomparison with any of the control cakes.

The reaction product of Examples 11 and IV Were also evaluated by addingthe reaction product to a liquid vegetable oil at the below-indicatedpercentages with 2.5 percent hydrogenated (LV. less than 1) fish oilmonoand di-glycerides (comprising about one-third C or greater fattyacid radicals in the mono-glycerides), and baking the standard Whitecake comprising the resultant mixture. The procedure used in preparingthe cake was identical to the procedure set forth hereinbefore. Table 2summarizes the results of this evaluation.

TABLE 2.BAKING PERFORMANCE WITH LIQUID It will be seen that theresultant cakeshad volume, profile, grain and texture comparable to thebest control cakes set forth in Table 1. In addition, the cakes hadexcellent eating qualities, being tender and moist.

Cakes baked in accordance with any of the foregoing liquid shorteningexamples utilizing 2.5 percent glycerol last-o palmitate in place of thefish oil monoglycerides are also of excellent quality, with good grainand texture, volume and profile.

The presence of long chain length saturated monoglycerides providesliquid shortenings with excellent properties. In this connection, it hasbeen found that chain length greater than C gives superior results.

Example VI In accordance with this example, a succinyl half ester ofmono-behenin is prepared. In the preparation of the succinyl half ester98 grams of distilled mono-behenin was reacted with 24 grams of succinicanhydride at a temperature of 170 C. for 45 minutes. At the end of thereaction, the acid number of the product was 98.5. The product of thereaction was washed with water at 85 degrees C. and the reaction wasdried and resulted in a hard waxy product having a melting point of80-85 degrees C. The acid number of the product, after washing, was 74.g g

A liquid shortening was prepared with the succinyl half ester bydissolving it in refined cottonseed oil at a level of 2.5 percent. Inaddition, 2.5 percent of hardened fish oil monoglycerides was alsodissolved in the cottonseed oil.

Dissolution of the succinyl half ester and the monoi This liquid sh'ortening was compared to a like shortening, except that the succinyl halfester of mono-behenin was replaced by a succinyl half ester ofmono-stearin. Cakes baked with each of these liquid shortenings wereexcellent and were comparable.

Example VII 'In accordance with this example, a succinyl half ester isprepared under low temperature conditions, i.e., below the melting pointof succinic anhydride. 16,000 grams of distilled mono-stearin (Myverol1800) were melted in a three-necked flask equipped with a stirrer. Thetemperature of the mono-stearin was adjusted to 80 degrees C. Aftermelting, the mono-stearin was subjected to a vacuum for a short time toremove moisture. A nitrogen blanket was established over the melt and4,000 grams of succinic anhydride and 80 grams of potassium stearatewere added. A heterogeneous mixture of a liquid and solid phase wasformed and was stir-red. The temperature was controlled at 80 degrees C.and, 1 hour and 30 min utes after the addition of the succinicanhydride, the solution became homogeneous. The reaction was allowed toproceed for additional minutes, whereupon the solution was cooled to 70degrees C. and spray chilled through a nozzle under a pressure of 30p.s.i.g. into a fine powder which had an average particle size of 30microns. The reaction product had an acid number of 116.4 and aFischer-John melting point of 59-62 degrees C. The reaction productcontained 1.7 percent of free succinic acid and less than 50 parts permillion (ppm) of succinic anhydride.

A liquid shortening was prepared by taking 57.5 pounds of winterizedcottonseed oil which had been deodorized for one hour at 510 degrees F.During cooling of the oil, citric acid was introduced to a concentrationof .01 percent, when the oil temperature was at about 320 degrees F. Tothis oil was added 3 pounds of an emulsifier melt at 250 degrees F. Theemulsifier melt comprised 1.5 pounds of the above-prepared succinyl halfester, 1.35

pounds of glycerol lacto palmitate and .15 pounds of distilledmono-stearin (Myverol 1 807). The emulsifier melt at about 250 degreesF. was added to the oil and the temperature of the resulting mixture wasmaintained at 220-250 degrees F. for about 10 minutes. This temperaturewas then dropped to 150 degrees F. and the liquid shortening was placedin a kettle and held, with slow agitation, at 9 2 degrees F. for onehour. An antioxidant was added to the liquid shortening, the antioxidantbeing Tennox IV, at a levcl of .5 percent. The liquid shortening waspassed through a swept surface heat exchanger and exited at atemperature of about 50 degrees F. The liquid shortening was filled intoglass jars. The liquid shortening was utilized in the preparation ofhigh ratio cakes and produced cakes of high volume with good crusts andgrain. There was no flavor detected in either the shortening or thecakes, which could be attributed to the presence of undesirablecondensation products of succinic anhydride.

Example VIII A number of samples of succinyl half ester were prepared atvarious reaction temperatures and with various catalytic conditions.Each sample was prepared by melting 500 grams of mono-stearin sold underthe trade name Myverol 1800. This product comprises at least about 90percent monoglyceride. Each sample was introduced into a three-neckedflask provided with a mechanical agitator, temperature control means,and an inlet and outlet for nitrogen gas in order to conduct thereaction in the flask under inert conditions. The mono-stearin wasmelted and the temperature adjusted to a temperature below the meltingpoint of succinic anhydride, as set forth in Table 3. As also set forthin Table 3, the catalyst was added at a particular level and 125'g'rarnsof succinic anhydride was also added. The molar ratio of monostearin tosuccinic anhydride was about 12.95.

The time of reaction was measured from the time of addition of thecatalyst and the end point of the reaction was determined by substantialdisappearance of the succinic anhydride. After completion of thereaction, the reaction mixture was poured into a cooling pan and allowedto cool to room temperature. The results of the reaction are set forthin the following table:

TABLE 3 40 Reaction Reaction Acid Sample Catalyst, percent of Tempera-Time, Number monostearin ture, C. minutes of Product 1 0.1% K 003 110116 50 2 0.4% 100 120 120 3 0.1% K2COa. 90 100 127 4 0.1% 45 130 5 0.1%80 105 121 0.2% K2003 1.. 8O 119 0.2% potassium mono- 00 118 succinate.0.3% potassium mono- 90 122 succinate. 0.5% potassium salt of 80 118. 5

monostearin halt ester of succinic acid. 10. 0.2% NayCOs 80 80 122 0.3%calcium acetate 80 132 1% calcium stearatc- 80 120 124 A control samplewas prepared at a reaction temperature of 115 degrees C. and thereaction proceeded to completion in minutes. The end product had an acidnumber of 118. The control sample was prepared in the same way as thesamples set forth in the above table.

Example IX 1 1 was stirred under a nitrogen blanket and the temperaturewas controlled at about 82 degrees C.

After 1 hour and 45 minutes from the addition of the succinic anhydride,the mixture had become substantially homogeneous and the acid number was55. After two hours and 15 minutes from the addition of the succinicanhydride, the acid number had dropped to 46.6 and the reaction wasterminated. The mixture was passed through a swept surface heatexchanger and lowered in temperature to about degrees C. The mixture wasused in bread baking and gave bread of good volume, grain structure andsoftness.

Example X Succinyl half ester of the invention was used in thepreparation of breads which contained varying amounts of fat and varyingamounts of the half ester. The breads were made in accordance with astandard procedure in which a sponge was first prepared and was added toa dough mix. After baking of the bread, the grain of the bread wasexamined and the specific volume was determined. In addition, thesoftness of the bread was determined 24 hours and 72 hours after baking.The softness of the bread was determined by the method of the AmericanAssociation of Cereal Chemists entitled Staleness of Bread-Compressionof Firmness Test with Bloom Gelometer (Cereal Laboratory Methods, 1959,6th Edition, section 85.1b, p. 352. Published by American Association ofCereal Chemists, University Farm, St. Paul, Minn). Lower values indicatesofter bread. The results of the baking test with various compounds ofthis invention are set forth in the following table:

12 3. A liquid shortening comprising a half ester of succinic acid andof a mono-acylated polyhydric alcohol having the formula:

in which F is a residue of an even numbered, straight chain saturatedfatty acid having from 14 to 24 carbon atoms, SCOO is the residue ofsuccinic acid and A is a residue of a polyhydric alcohol having astraight chain length of from 2 to 6 carbon atoms, m is equal to 1 and nis a number from 0 to 4.

4. A liquid shortening comprising an edible oil and a half ester ofsuccinic acid and of a mono-acylated polyhydric alcohol having theformula:

in which F is a residue of a saturated fatty acid having an evennumbered carbon chain from 14 to 24 carbon atoms, SCOO is the residue ofsuccinic acid and A is a residue of propylene glycol, m is equal to 1and n is 1, said fatty compound being present in the liquid shorteningat a level in excess of about 3.5 percent.

5. A dough product comprising a half ester of succinic acid and of amono-acylated polyhydric alcohol having the formula:

A(OH) -(F )-(SCOOM) in which F is a residue of an even numbered,straight chain saturated fatty acid having from 14 to 24 carbon atoms,SCOO is the residue of succinic acid and A is a residue of a polyhydricalcohol having a straight chain length of from 2 to 6 carbon atoms, Inis equal to 1, 22

TABLE 4.--BREAD BAKING RESULTS Percent of Flour Specific ol'tnessEmulsifier Compound Grain Volume Lard Emulsifier 24 hours 72 hours 1.Suecinyl Half Ester of Mono-stearin .8 .3 5. 78 i 118 193- 2. CalciumSalt of Succinyl Half Ester of Mono- .8 .3 5.72 140 230 s earin.

3. Magnesium Salt of Suceinyl Half Ester of .8 .3 5.73 130 212Mono-steariu.

4. Succinyl Half Ester of Mono-stearin" 0 3 5. 59 117 180 5. SuccinylHalf Ester of Mono-stearin 0 .2 5. 57 136 212 6. Suecinyl Half Ester ofMono-stearin .1 0 1 5. 54 150 237 7. Sodium Salt of Suceinyl Half Esterof Mono- 0 .3 5. 61 127 203 stearin. 8. None- 0 .48 164 278 9. None H 31 5.78 139 220 i 10. Suecinyl Half Ester of Mono-stearin 3 .1 5. 68 139220 11. Suceinyl Hall Ester of Mono-stearin 3 5. 68 139 223 12. SuccinylHalf Ester of M0no-stcarin 3 .25 5.63 128 204 13. Succinyl Hall Ester ofMono-steariu 3 .5 5.78 111 168 It will be seen from the foregoing thatnew and unique is a number from 0 to 4, and M is hydrogen or an ediblecompounds have been provided which have particular alkali metal oralkaline earth. utility in respect to baked goods. 6. A bread doughincluding flour comprising a half The various features of this inventionwhich are believed ester of succinic acid and of a monoacylatedpolyhydric to be new are set forth in the following claims. alcoholhaving the formula:

What is claimed is: 1. A shortening comprising ahalf ester of succinicacid A( (Fm) (SCOOM) and f a mono acylated 1 d i l h l h i th in which F15 a residue of stearic acid, SCOO is the residue formula: of succinicacid and A is a residue of a polyhydric alcohol c Q having a straightchain length of from 2 to 6 carbon atoms m 's u 1n which F is a residueof an even numbered, straight is d g in lciibi e ifiiii ii i ik 1i and hchain saturated fatty acid having from 14 to 24 carsaid fatt com Oundbein re enteat ne eart bon atoms, SCOO is the residue of succinic acidand A about t based 5 2 w i i excess 0 is a residue of a polyhydricalcohol having a straight 6r p e o o 7. A bread dough including flourCOI'HPIISIIlg a half chain length of from 2 to 6 carbon atoms, m isequal ester of succinic acid and of 3 mon a 1 t d 1 h d to 1, n is anumber from 0 to 4, and M is hydrogen or alcohol havin the formula 0 Cya 6 P0 Y Y rlc an edible alkali metal or alkaline earth. g

2. A shortening comprising a ha.f es.er of succinic acid A(OH)D, (Fm)(SCOOH) and of a mono-acylated polyhydric alcohol having the formula: rin which F is a residue of stearic acid, SCOO is the residue A\ )n m)'(of succinic acid and A is residue of glycerol, m is equal in which F isa residue of stearic acid, SCOO is the residue to 1 and n 15 1, 531dfatty Compound being P in bread of succinic acid and A is a residue ofglycerol, m is equal at a level in excess of about .2 percent based uponthe to 1 and n is 1. weight of the flour.

13 8. A plastic shortening comprising a half ester of succinic acid andof a mono-acylated polyhydric alcohol having the formula:

in which F is a residue of an even numbered, straight chain saturatedfatty acid having from 14 to 24 carbon atoms, SCOO is the residue ofsuccinic acid and A is a residue of a polyhydric alcohol having astraight chain length of from 2 to 6 carbon atoms, m is equal to l and nis a number from 0 to 4.

9. A plastic shortening comprising a half ester of succinic acid and ofa mono-acylated polyhydric alcohol having the formula:

atoms, SCOO is the residue of succinic acid and A is a 20 residue of apolyhydric alcohol having a straight chain length of from 2 to 6 carbonatoms, In is equal to 1 and n in which F is a residue of stearic acid,SCOO is the residue of succinic acid and A is a residue of glycerol, inis equal to 1 and n is equal to 1, in combination with a sodium salt ofsuccinylated monoglyceride.

References Cited UNITED STATES PATENTS 2,552,706 5/1951 Bertram 99123 X3,145,107 8/1964 Howard 99-118 3,145,108 8/1964 Howard 991l8 3,145,1098/1964 Howard 99-118 FOREIGN PATENTS 652,006 4/ 1951 Great Britain.

MAURICE W. GREENSTEIN, Primary Examiner.

1. A SHORTENING COMPRISING A HALF ESTER OF SUCCINIC ACID AND OF AMONO-ACYLATED POLYHYDRIC ALCOHOL HAVING THE FORMULA: